US3717525A - Method for production of a diffusion membrane arrangement - Google Patents

Method for production of a diffusion membrane arrangement Download PDF

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Publication number
US3717525A
US3717525A US00731386A US3717525DA US3717525A US 3717525 A US3717525 A US 3717525A US 00731386 A US00731386 A US 00731386A US 3717525D A US3717525D A US 3717525DA US 3717525 A US3717525 A US 3717525A
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Prior art keywords
membrane
carrier
diffusion
diffusion membrane
porous
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Expired - Lifetime
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US00731386A
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English (en)
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H Bueltemann
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Varian Mat GmbH
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Varian Mat GmbH
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01M—TESTING STATIC OR DYNAMIC BALANCE OF MACHINES OR STRUCTURES; TESTING OF STRUCTURES OR APPARATUS, NOT OTHERWISE PROVIDED FOR
    • G01M3/00—Investigating fluid-tightness of structures
    • G01M3/02—Investigating fluid-tightness of structures by using fluid or vacuum
    • G01M3/04—Investigating fluid-tightness of structures by using fluid or vacuum by detecting the presence of fluid at the leakage point
    • G01M3/20—Investigating fluid-tightness of structures by using fluid or vacuum by detecting the presence of fluid at the leakage point using special tracer materials, e.g. dye, fluorescent material, radioactive material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J41/00—Discharge tubes for measuring pressure of introduced gas or for detecting presence of gas; Discharge tubes for evacuation by diffusion of ions

Definitions

  • the invention is concerned with a method of making gas diffusion membranes.
  • the pores adjacent the surface of a porous permeable carrier member are filled with a material, later to be removed, a diffusion member is applied to that surface, and the filler material is then removed.
  • a diffusion member is applied to a glass carrier member which is pore-free, and the glass is then made porous by heat treatment and selective dissolution.
  • the invention relates to a diffusion membrane arrangement, more particularly for leakage detector tubes with a selectively permeable membrane window and measurement by ionisation and ion current measurements.
  • the gas permeability of membranes increases in inverse proportion to the membrane thickness and exponentially with the membrane temperature. If a high gas permeability is to be achieved, then the membrane must be made as thin as possible, since the temperature cannot be made arbitrarily high.
  • quartz is selectively permeable for helium, and palladium for hydrogen.
  • Methods for production of thin membranes are known, for example quartz membranes with thicknesses to as little as 1 mm. Such membranes are however extremely sensitive to breakage.
  • This problem is solved according to the invention in that the diffusion membrane is provided on a porous permeable carrier.
  • the possibility is given of making the membrane thickness extremely small and thus achieving a high gas permeability, but simultaneously avoiding the hitherto high sensitivity of the membranes to fracture.
  • the membrane material can be applied in a layer free of pores on a carrier for example by vaporisation.
  • a carrier for example by vaporisation.
  • other known methods can be used, with which very thin layers can be formed on carrier bodies, e.g. by depositing by means of ion atomisation, plasma atomisation and so on.
  • an auxiliary carrier with a smooth surface can be used, from which, after formation, the membrane can be released and then connected with the porous permeable carrier.
  • the auxiliary carrier after application of the membrane material can be dissolved by a solvent which easily dissolves the auxiliary carrier but does not dissolve the membrane material.
  • the porous permeable carrier is itself used. If in this case the width of the pores of the carrier is sufficiently small, penetration of the membrane material into the pores of the carrier surface when applying the membrane layer is avoided, or is kept to allowable limits. With larger pore widths, the remedy can be adopted that the pores of the carrier are closed by a covering or filling material before applying the membrane material, and after application of the membrane material the filler is removed, at least in the region of the pores. After closing of the pores by the covering or filling material, the carrier is advantageously smoothed. As a covering or filling material a material can be used which melts or evaporates at a lower temperature than the material of the carrier and can be brought into a liquid or vaporous phase.
  • the filling material After applying the membrane, the filling material can be converted into a liquid or gaseous condition by chemical reaction and drawn off, or it can be dissolved by means of a solvent.
  • the surface layer of the porous permeable carrier by suitable surface treatment can itself be converted into a nonporous layer which forms the diffusion membrane, in that the surface is for example treated by electron impact or ion impact or by laser radiation.
  • FIG. 1 is a diagrammatic sectional view of a leakage detector tube with a diffusion membrane arrangement ac-- cording to the invention
  • FIG. 2 is a partial cross-section through a diffusion membrane arrangement on a leakage detector tube, to a larger scale than FIG. 1;
  • FIG. 3 is a cross-section through a membrane arrangement according to the invention, for illustrating a method of production of such an arrangement
  • FIG. 4 is a partial section through a diffusion membrane for another embodiment of the membrane arrangement.
  • FIG. 5 is a partial cross-section through a leakage detector tube, having a membrane arrangement with a membrane according to FIG. 4.
  • a leakage detector tube of conventional construction is diagrammatically illustrated as an example of use for the diffusion membrane arrangements according to the invention.
  • a leakage detector tube comprises of a vacuum chamber 1 in a wall 2 of which a window 3 with a difiusion membrane 4 of increased permeability for preferred diffusion of a test gas to the inner chamber 1 of the tube, is provided.
  • an ionisation manometer 5 is provided which is connected through an electric line 6 with an electric indication device, not illustrated in the drawing.
  • a heating coil 7 is provided for heating the diffusion membrane 4.
  • the diffusion membrane 4 is provided on a porous permeable carrier 8.
  • a porous permeable carrier 8 By this provision of the diffusion membrane on the carrier, it is possible to give the diffusion membrane a very small thickness of e.g. 3 mm., since the membrane receives the necessary support by the porous carrier and the danger of destruction by mechanical overloading is substantially removed.
  • the illustrated leakage detector tube can be moved along pressure vessels filled with test gas, for locating small leakage regions in the pressure vessels.
  • the diffusion membrane advantageously consists of quarts, which is selectively permeable for helium.
  • quartz is also suitable, for example the kind which is available as filter glass under the designation Vycorbrand No. 7930 (see Werkstolftechnik by Dr. Werner Espe, volume 2 pages 451-453 VEB Deutsche Verlag dermaschineen Berlin 1962).
  • the diffusion membrane 4 can be placed on the inside of the vacuum chamber 1, as illustrated in FIG. 1. Thereby, the diffusion membrane is particularly well protected against mechanical stresses.
  • the diffusion membrane 4 is placed on the outside of the tube, as illustrated in FIG. 2, in order to bring it into as intimate contact as possible with the test gas emerging from the leakage regions.
  • the diffusion membrane 4 can then be covered with a protective grid 9.
  • the diffusion membrane can form a surface layer fixedly connected with the porous permeable carrier 8, as assumed in the embodiments of FIGS. 1, 2 and 3; it can alternatively, as illustrated in FIGS. 4 and 5, consist of a separate part and lie loosely on the porous permeable carrier.
  • the diffusion membrane 4 is preferably connected with a reinforced rim or mounting ring 10.
  • the membrane material can for example be vaporised onto the carrier in the form of a thin pore-free layer, or can be applied by known methods of ion atomising and plasma atomising.
  • this application of the membrane material is effected onto an auxiliary carrier, e.g. in the form of a thin plate 11, see FIG. 4, which is surrounded by the mounting ring 10 for the finished membrane.
  • the membrane material is then applied in the described manner onto the common lower surface of the auxiliary carrier 11 and mounting ring 10. After this has occurred, the diffusion membrane 4 together with the mounting ring 10 is released from the auxiliary carrier 11 and for example in the manner visible from FIG. 5 is connected with the porous permeable carrier 3.
  • the releasing of the difiusion membrane 4 with its mounting ring 16 from the auxiliary carrier 11 can take place in such a manner that the auxiliary carrier 11 after application of the membrane material is dissolved by a suitable solvent which readily dissolves the auxiliary carrier but does not dissolve the membrane material.
  • the auxiliary carrier 11 can consist of copper and can be dissolved for example by sulphuric acid, which does not attack quartz.
  • the diffusion membrane 4 fixedly connected with the mounting ring is placed loosely in the window of the chamber 1, so that it comes to lie on the porous permeable carrier 8.
  • the protective grid 9 is then applied and the membrane with its mounting ring 10 is secured in its proper position and closed in a vacuum tight manner, so that gas can simply pass through the membrane 4 and the porous carrier 8, into the vacuum chamber 1.
  • the diffusion membrane 4 is applied directly onto the porous permeble carrier 8 itself, then the pores of the carrier, insofar as their width would result in an inadmissible penetration of the membrane material during application, are closed before the application of the membrane material by a covering or filling material, e.g. tin, indium or an alloy of these materials.
  • a covering or filling material e.g. tin, indium or an alloy of these materials.
  • the membrane material is then applied to the flattened surface and 4 thereafter the filling material 12 is caused to disappear in that for example it is dissolved in a solvent or is converted into the liquid or gaseous state and is drawn off.
  • nitrohydrochloric acid can be used.
  • a body As a carrier for the membrane material, alternatively a body can be used which at first is free of pores, and after application of the membrane material is rendered porous by releasing a component in known manner from the side which is not covered.
  • Particularly suitable for the present purpose is a glass material which can be separated by heat treatment into two phases, a soluble and an insoluble phase, as in the production of the above mentioned Vycorbrand glasses as an intermediate product of a glass having the approximate composition SiO 20% B 0 and 5% alkali oxide.
  • the material (B 0 and Na O) filling the pores of the skeleton is dissolved in hot 3 n-HCl or 5 n-H SO until only the 'SiO;; skeleton with the diffusion membrane covering one side, which likewise can consist of SiO;, remains.
  • the surface layer of the porous permeable carrier can also be converted by surface treatment into the nonporous layer forming the diffusion membrane.
  • This conversion of the surface layer is effected preferably by radiation with a high specific energy, e.g. by means of electron impact or ion impact or laser.
  • the illustrated diffusion membrane arrangement is not only usable for leakage detector tubes, but is advantageous also for other purposes, for example for introducing or removing a component from a gas mixture, for separating the carrier gas from a gas chromatographic column and for gas analysis or partial pressure measurement of a gas current fed to a mass spectrometer or ionisation manometer.
  • a membrane with a reinforced rim similar to that illustrated in FIGS. 4 and 5, can also be formed by more intensive vaporisation in the marginal zone, when depositing the membrane material.
  • a method for production of a diffusion membrane arrangement comprising:
  • said filling material being soluble in a solvent which is non-reactive with said carrier or said membrane;
  • a method for production of a diffusion membrane comprising:
  • a carrier member having a surface thereof of predetermined contour, said carrier member being substantially pore-free and being formed from glass which is separable by heat treatment into a soluble phase and an insoluble phase, said insoluble phase defining a skeletal, porous structure;
  • a thin, pore-free diffusion membrane made from a relatively brittle material and having a' surface of substantially identical contour to that of'said surface of said carrier member to said surface of said carrier member;
  • a method for production of a difiusion membrane arrangement comprising:

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Examining Or Testing Airtightness (AREA)
  • Surface Treatment Of Glass (AREA)
US00731386A 1967-06-05 1968-05-23 Method for production of a diffusion membrane arrangement Expired - Lifetime US3717525A (en)

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Application Number Priority Date Filing Date Title
DEB0092867 1967-06-05

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US (1) US3717525A (enrdf_load_stackoverflow)
DE (1) DE1648367A1 (enrdf_load_stackoverflow)
FR (1) FR1580255A (enrdf_load_stackoverflow)
GB (1) GB1235488A (enrdf_load_stackoverflow)

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3874899A (en) * 1971-08-24 1975-04-01 Montedison Spa Process for the preparation of porous membranes or composite barriers for gaseous diffusion installations
US4340615A (en) * 1979-06-07 1982-07-20 The Medishield Corporation Limited Apparatus for analysis of absorbed gases
US4410338A (en) * 1979-06-25 1983-10-18 Kabushiki Kaisha Toyota Chuo Kenkyusho Gas separating members and a method of making the same
US4581043A (en) * 1983-08-02 1986-04-08 Shell Oil Company Composite dense membrane
US4589891A (en) * 1983-09-08 1986-05-20 Kernforschungsanlage Julich Gesellschaft Mit Beschrankter Haftung Hydrogen permeatin membrane, process for its manufacture and use
US4902307A (en) * 1988-11-18 1990-02-20 California Institute Of Technology Synthesis of SiO2 membrane on porous support and method of use of same
US5753014A (en) * 1993-11-12 1998-05-19 Van Rijn; Cornelis Johannes Maria Membrane filter and a method of manufacturing the same as well as a membrane
US5827569A (en) * 1994-07-29 1998-10-27 Akiyama; Shigeo Hydrogen separation membrane and process for producing the same
US6039792A (en) * 1997-06-24 2000-03-21 Regents Of The University Of California And Bp Amoco Corporation Methods of forming and using porous structures for energy efficient separation of light gases by capillary condensation
US6315820B1 (en) * 1999-10-19 2001-11-13 Ford Global Technologies, Inc. Method of manufacturing thin metal alloy foils
US6572683B2 (en) * 2000-11-24 2003-06-03 Sumitomo Electric Industries, Ltd. Substance separation structure and method of preparing the same
US20030233940A1 (en) * 2002-06-07 2003-12-25 Hideaki Takatani Hydrogen separation membrane, hydrogen separation unit, and manufacturing method for hydrogen separation membrane
WO2004085044A1 (en) * 2003-03-21 2004-10-07 Worcester Polytechnic Institute Method for fabricating composite gas separation modules
US20040244590A1 (en) * 2003-05-02 2004-12-09 Worcester Polytechnic Institute Composite gas separation modules having high Tamman temperature intermediate layers
US20050113316A1 (en) * 2001-07-24 2005-05-26 Panagin Pharmaceuticals Inc. Process for producing dammarane sapogenins and ginsenosides
US20060016332A1 (en) * 2004-07-21 2006-01-26 Ma Yi H Composite gas separation modules having a layer of particles with a uniform binder metal distribution
US20100132546A1 (en) * 2007-04-05 2010-06-03 Yi Hua Ma Composite Structures with Porous Anodic Oxide Layers and Methods of Fabrication
US20110247498A1 (en) * 2010-04-09 2011-10-13 Vladimir Schwartz Gas-selective membrane and method of its production
US8652239B2 (en) 2010-05-03 2014-02-18 Worcester Polytechnic Institute High permeance sulfur tolerant Pd/Cu alloy membranes
US10092911B2 (en) * 2013-12-05 2018-10-09 Yuemeng Liu Centrifuge filter tube

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56126733A (en) * 1980-03-10 1981-10-05 Nippon Sanso Kk Detecting method for leakage of helium
IT1393996B1 (it) * 2008-09-18 2012-05-17 Univ Degli Studi Genova Dispositivo di fuga di riferimento per la calibrazione delle perdite
CN119285175B (zh) * 2024-12-10 2025-03-07 自然资源部天津海水淡化与综合利用研究所 一种海水养殖尾水处理的过滤分离系统

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3874899A (en) * 1971-08-24 1975-04-01 Montedison Spa Process for the preparation of porous membranes or composite barriers for gaseous diffusion installations
US4340615A (en) * 1979-06-07 1982-07-20 The Medishield Corporation Limited Apparatus for analysis of absorbed gases
US4410338A (en) * 1979-06-25 1983-10-18 Kabushiki Kaisha Toyota Chuo Kenkyusho Gas separating members and a method of making the same
US4581043A (en) * 1983-08-02 1986-04-08 Shell Oil Company Composite dense membrane
US4589891A (en) * 1983-09-08 1986-05-20 Kernforschungsanlage Julich Gesellschaft Mit Beschrankter Haftung Hydrogen permeatin membrane, process for its manufacture and use
US4902307A (en) * 1988-11-18 1990-02-20 California Institute Of Technology Synthesis of SiO2 membrane on porous support and method of use of same
US5753014A (en) * 1993-11-12 1998-05-19 Van Rijn; Cornelis Johannes Maria Membrane filter and a method of manufacturing the same as well as a membrane
US5827569A (en) * 1994-07-29 1998-10-27 Akiyama; Shigeo Hydrogen separation membrane and process for producing the same
US6039792A (en) * 1997-06-24 2000-03-21 Regents Of The University Of California And Bp Amoco Corporation Methods of forming and using porous structures for energy efficient separation of light gases by capillary condensation
US6315820B1 (en) * 1999-10-19 2001-11-13 Ford Global Technologies, Inc. Method of manufacturing thin metal alloy foils
US6572683B2 (en) * 2000-11-24 2003-06-03 Sumitomo Electric Industries, Ltd. Substance separation structure and method of preparing the same
US20050113316A1 (en) * 2001-07-24 2005-05-26 Panagin Pharmaceuticals Inc. Process for producing dammarane sapogenins and ginsenosides
US20030233940A1 (en) * 2002-06-07 2003-12-25 Hideaki Takatani Hydrogen separation membrane, hydrogen separation unit, and manufacturing method for hydrogen separation membrane
US7144444B2 (en) * 2002-06-07 2006-12-05 Mitsubishi Heavy Industries, Ltd. Hydrogen separation membrane, hydrogen separation unit, and manufacturing method for hydrogen separation membrane
WO2004085044A1 (en) * 2003-03-21 2004-10-07 Worcester Polytechnic Institute Method for fabricating composite gas separation modules
US20040237780A1 (en) * 2003-03-21 2004-12-02 Worcester Polytechnic Institute Method for fabricating composite gas separation modules
US7390536B2 (en) 2003-03-21 2008-06-24 Worcester Polytechnic Institute Method for fabricating composite gas separation modules
US20040244590A1 (en) * 2003-05-02 2004-12-09 Worcester Polytechnic Institute Composite gas separation modules having high Tamman temperature intermediate layers
US7255726B2 (en) 2003-05-02 2007-08-14 Worcester Polytechnic Institute Composite gas separation modules having high Tamman temperature intermediate layers
US20060016332A1 (en) * 2004-07-21 2006-01-26 Ma Yi H Composite gas separation modules having a layer of particles with a uniform binder metal distribution
US7727596B2 (en) 2004-07-21 2010-06-01 Worcester Polytechnic Institute Method for fabricating a composite gas separation module
US20100132546A1 (en) * 2007-04-05 2010-06-03 Yi Hua Ma Composite Structures with Porous Anodic Oxide Layers and Methods of Fabrication
US8366805B2 (en) 2007-04-05 2013-02-05 Worcester Polytechnic Institute Composite structures with porous anodic oxide layers and methods of fabrication
US20110247498A1 (en) * 2010-04-09 2011-10-13 Vladimir Schwartz Gas-selective membrane and method of its production
US8361196B2 (en) * 2010-04-09 2013-01-29 Inficon Gmbh Gas-selective membrane and method of its production
US8425672B2 (en) * 2010-04-09 2013-04-23 Inficon Gmbh Gas-selective membrane and method of its production
US8652239B2 (en) 2010-05-03 2014-02-18 Worcester Polytechnic Institute High permeance sulfur tolerant Pd/Cu alloy membranes
US10092911B2 (en) * 2013-12-05 2018-10-09 Yuemeng Liu Centrifuge filter tube

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FR1580255A (enrdf_load_stackoverflow) 1969-09-05
GB1235488A (en) 1971-06-16
DE1648367A1 (de) 1971-04-15

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